Substituted aza(cyclo)alkanes

ABSTRACT

Insecticidal substituted diazacyclohexanes of the formula  &lt;IMAGE&gt; in which R1 is a heterocyclic radical, R4 is a hydrogen or an organic radical.

This is a division of application Ser. No. 08/139,350, filed on Oct. 20,1993 now U.S. Pat. No. 5,461,069.

The invention relates to novel substituted aza(cyclo)alkanes, processesfor their preparation and their use as agents for combating pests, inparticular as insecticides.

It is already known that certain heterocyclic compounds possessinsecticidal properties (cf. EP-A 192 060).

The novel substituted aza(cyclo)alkanes of the general formula (I) havenow been found ##STR2## in which R¹ represents a five- or six-memberedheterocyclic grouping, which contains 1, 2, 3 or 4 nitrogen atoms and/orone or two oxygen atoms or sulphur atoms as the heteroatom ringmembers--the number of heteroatoms being 1, 2, 3 or 4--and which isoptionally substituted by halogen, cyano, nitro, alkyl, halogenoalkyl,alkenyl, halogenoalkenyl, alkinyl, alkoxy, halogenoalkoxy, alkenyloxy,halogenoalkenyloxy, alkinyloxy, alkylthio, halogenoalkylthio,alkenylthio, halogenoalkenylthio, alkinylthio, alkylsulphinyl,halogenoalkylsulphinyl, alkylsulphonyl, halogenoalkylsulphonyl, amino,alkylamino, dialkylamino, aryl, arylthio, arylamino, aralkyl,formylamino, alkylcarbonylamino, formyl, carbamoyl, alkylcarbonyl and/oralkoxycarbonyl,

R² represents hydroxyalkyl, polyhydroxyalkyl, alkoxyalkyl orpolyalkoxyalkyl,

R³ represents hydrogen, alkyl, hydroxyalkyl, dihydroxyalkyl, alkoxyalkylor dialkoxyalkyl,

R² and R³ together represent hydroxyalkanediyl, dihydroxyalkanediyl,alkoxyalkanediyl, dialkoxyalkanediyl, oxoalkanediyl or dioxoalkanediyl,

R⁴ represents hydrogen, alkyl (which is optionally substituted byhalogen, cyano, alkoxy, alkylthio, dialkylamino, trialkylsilyl,alkoxycarbonyl, carboxyl, carbamoyl, alkylaminocarbonyl ordialkylaminocarbonyl, or by the radical R¹, where R¹ has theabovementioned meaning), alkenyl (which is optionally substituted byhalogen), alkinyl, benzyl (which is optionally substituted by halogen,cyano, nitro, alkyl, halogenoalkyl, alkoxy or alkoxycarbonyl), formyl,alkylcarbonyl (which is optionally substituted by halogen, cyano,phenyl, phenoxy or alkoxy), cycloalkylcarbonyl (which is optionallysubstituted by halogen and/or alkyl), alkenylcarbonyl (which isoptionally substituted by halogen), phenylcarbonyl or naphthylcarbonyl(which are optionally substituted by halogen, alkyl, halogenoalkyl,cyano, nitro, alkoxy and/or lalkoxycarbonyl), alkoxycarbonyl,benzyloxycarbonyl, phenoxycarbonyl, alkylthiocarbonyl,benzylthiocarbonyl, phenylthiocarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl, phenylaminocarbonyl (which is optionallysubstituted by halogen, cyano, nitro, alkyl, halogenoalkyl, alkoxy,halogenoalkoxy, alkylthio, halogenoalkylthio or alkoxycarbonyl),benzoylaminocarbonyl (which is optionally substituted by halogen, alkylor halogenoalkyl), phenylsulphonylaminocarbonyl (which is optionallysubstituted by halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy oralkoxycarbonyl), alkylthio (which is optionally substituted by halogen),phenylthio (which is optionally substituted by halogen, nitro or alkyl),alkylsulphinyl, alkylsulphonyl (which is optionally substituted byhalogen), phenylsulphinyl (which is optionally substituted by halogen,nitro or alkyl), phenylsulphonyl or naphthylsulphonyl (which areoptionally substituted by halogen, cyano, nitro, alkyl, halogenoalkyl,alkoxy, halogenoalkoxy and/or alkoxycarbonyl), dialkyl(thio)phosphoryl,alkylalkoxy-(thio)phosphoryl or dialkoxy(thio)phosphoryl,

Y represents nitrogen or a CH group and

Z represents cyano or nitro.

The novel substituted aza(cyclo)alkanes of the general formula (I) areobtained if

(a) azaalkanes of the general formula (II) ##STR3## in which R¹, Y and Zhave the abovementioned meaning, are reacted with halogen compounds ofthe general formula (IIIa)

    X--R.sup.2                                                 (IIIa)

and/or halogen compounds of the general formula (IIIb)

    X--R.sup.3                                                 (IIIb)

in which

R² and R³ have the abovementioned meaning and

X represents halogen, optionally in the presence of an acid acceptor,optionally in the presence of a catalyst or optionally in the presenceof a diluent, or if

(b) compounds of the general formula (I), in which R² or R³ representsdialkoxyalkyl and R¹, R⁴, Y and Z have the abovementioned meaning, areheated, optionally in the presence of a reaction aid and optionally inthe presence of a diluent, or if

(c) compounds of the general formula (I), in which R² and R³ togetherrepresent oxoalkanediyl and R¹, R⁴, Y and Z have the abovementionedmeaning, are reacted with an hydrogenating agent, optionally in thepresence of a reaction aid and optionally in the presence of a diluent,or if

(d) compounds of the general formula (I), in which R² and R³ togetherrepresent alkoxyalkanediyl or dialkoxyalkanediyl and R¹, R⁴, Y and Zhave the abovementioned meaning, are reacted with a hydrogen halideand/or an alkali metal halide as well as in the presence of diluents, orif

(e) compounds of the general formula (I), in which R² and R³ togetherrepresent hydroxyalkanediyl or dihydroxyalkanediyl and R¹, R⁴, Y and Zhave the abovementioned meaning, are reacted with an alkylating agent ofthe general formula (IV)

    X.sup.1 --R                                                (IV)

in which

R represents alkyl and

X¹ represents halogen or the grouping --O--SO₂ --O--R in which R has theabovementioned meaning, optionally in the presence of an acid bindingagent and optionally in the presence of a diluent, or if

(f) compounds of the general formula (I), in which R⁴ representshydrogen and R¹, R², R³, Y and Z have the abovementioned meaning, arereacted with halogen compounds of the general formula (V)

    X--R.sup.4                                                 (V)

in which

X represents halogen and

R⁴ has, with the exception of hydrogen, the abovementioned meaning,optionally in the presence of an acid acceptor and optionally in thepresence of a diluent.

The novel substituted aza(cyclo)alkanes of the general formula (I) aredistinguished by their high activity as insecticides.

The invention relates preferably to compounds of the formula (I) inwhich

R¹ represents a five- to six-membered heterocyclic grouping from theseries comprising furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl,1,2,3- or 1,2,4-triazolyl, oxazolyl, isoxazolyl, 1,2,4- or1,3,4-oxadiazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,2,4-, 1,2,5- or1,3,4-thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl and pyrazinyl,which is optionally substituted by fluorine, chlorine, bromine, iodine,cyano, nitro, C₁ -C₄ -alkyl (which is optionally substituted by fluorineand or chlorine), C₂ -C₄ -alkenyl (which is optionally substituted byfluorine and/or chlorine), C₂ -C₄ -alkinyl, C₁ -C₄ -alkoxy (which isoptionally substituted by fluorine and/or chlorine), C₃ -C₄ -alkenyloxy(which is optionally substituted by fluorine and/or chlorine), C₃ -C₄-alkinyloxy, C₃ -C₄ -alkylthio (which is optionally substituted byfluorine and/or chlorine), C₃ -C₄ -alkenylthio (which is optionallysubstituted by fluorine and/or chlorine), C₃ -C₄ -alkinylthio, C₁ -C₄-alkylsulphinyl (which is optionally substituted by fluorine and/orchlorine), C₁ -C₄ -alkylsulphonyl (which is optionally substituted byfluorine and/or chlorine), amino, C₁ -C₄ -alkylamino, di-(C₁ -C₄-alkyl)-amino, phenyl, phenoxy, phenylthio, phenylamino, benzyl,formylamino, C₁ -C₄ -alkyl-carbonylamino, formyl, carbamoyl, C₁ -C₄-alkylcarbonyl and/or C₁ -C₄ -alkoxy-carbonyl,

R² represents C₁ -C₆ -hydroxyalkyl, dihydroxy-C₁ -C₆ -alkyl, C₁ -C₄-alkoxy-C₁ -C₄ -alkyl or di-(C₁ -C₄ -alkoxy)-C₂ -C₄ -alkyl,

R³ represents hydrogen, C₁ -C₆ -alkyl, C₁ -C₆ -hydroxyalkyl,dihydroxy-C₁ -C₆ -alkyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl or di-(C₁ -C₄-alkoxy)-C₁ -C₄ -alkyl, or

R² and R³ together represent hydroxy-C₂ -C₄ -alkanediyl, dihydroxy-C₂-C₄ -alkanediyl, C₁ -C₄ -alkoxy-C₂ -C₄ -alkanediyl, di-(C₁ -C₄-alkoxy)-C₂ -C₄ -alkanediyl, oxo-C₂ -C₄ -alkanediyl or dioxo-C₂ -C₄-alkanediyl,

R⁴ represents hydrogen, C₁ -C₄ -alkyl (which is optionally substitutedby fluorine, chlorine, cyano, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, di-(C₁-C₄ -alkyl)-amino. Trimethylsilyl, C₁ -C₄ -alkoxy-carbonyl, carboxyl,carbamoyl, C₁ -C₄ -alkyl-aminocarbonyl, di-(C₁ -C₃-alkyl)-aminocarbonyl, or by a heterocyclic grouping as is preferablydefined above for R¹ (including the possible substituents)), C₂ -C₄-alkenyl (which is optionally substituted by fluorine or chlorine), C₂-C₄ -alkinyl, benzyl (which is optionally substituted by fluorine,chlorine, cyano, nitro, C₁ -C₂ -alkyl, trifluoromethyl, C₁ -C₂ -alkoxyor C₁ -C₂ -alkoxycarbonyl), formyl, C₁ -C₂₀ -alkyl-carbonyl, (which isoptionally substituted by fluorine, chlorine, bromine, phenyl, phenoxyor C₁ -C₄ -alkoxy), C₃ -C₆ -cycloalkylcarbonyl (which is optionallysubstituted by fluorine, chlorine and/or C₁ -C₄ -alkyl), C₂ -C₂₀-alkenyl-carbonyl (which is optionally substituted by fluorine and/orchlorine), phenylcarbonyl or naphthylcarbonyl (which are optionallysubstituted by fluorine, chlorine, bromine, C₁ -C₄ -alkyl,trifluoromethyl, cyano, nitro, C₁ -C₄ -alkoxy and/or C₁ -C₄-alkoxy-carbonyl), C₁ -C₂₀ -alkoxy-carbonyl, benzyloxycarbonyl,phenoxyarbonyl, C₁ -C₄ -alkylthiocarbonyl, benzylthio-carbonyl,phenylthio-carbonyl, C₁ -C₆ -alkylamino-carbonyl, di-(C₁ -C₄-alkyl)-amino-carbonyl, phenylamino-carbonyl (which is optionallysubstituted by fluorine, chlorine, bromine, cyano, nitro, C₁ -C₄ -alkyl,trifluoromethyl, C₁ -C₄ -alkoxy, C₁ -C₂ -fluoroalkoxy, C₁ -C₂-chlorofluoroalkoxy, C₁ -C₄ -alkylthio, C₁ -C₂ -fluoroalkylthio, C₁ -C₂-chlorofluoroalkylthio or C₁ -C₄ -alkoxycarbonyl), benzoylamino-carbonyl(which is optionally substituted by fluorine, chlorine, bromine, methylor trifluoromethyl), phenylsulphonylamino-carbonyl (which is optionallysubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, C₁-C₄ -alkoxy, C₁ -C₂ -fluoroalkoxy, C₁ -C₂ -chlorofluoroalkoxy or C₁ -C₄-alkoxy-carbonyl), C₁ -C₄ -alkylthio (which is optionally substituted byfluorine and/or chlorine), phenylthio (which is optionally substitutedby fluorine, chlorine, bromine, nitro or methyl), C₁ -C₄-alkylsulphinyl, C₁ -C₄ -alkylsulphonyl (which is optionally substitutedby fluorine and/or chlorine), phenylsulphinyl (which is optionallysubstituted by fluorine, chlorine, bromine, nitro or methyl),phenylsulphonyl or naphthylsulphonyl (which are optionally substitutedby fluorine, chlorine, bromine, cyano, nitro, methyl, trifluoromethyl,C₁ -C₄ -alkoxy, C₁ -C₂ -fluoroalkoxy, C₁ -C₂ -chlorofluoroalkoxy and/orC₁ -C₄ -alkoxycarbonyl), dimethyl(thio)phosphoryl, C₁ -C₄ -alkyl-C₁ -C₄-alkoxy-(thio)phosphoryl or di(C₁ -C₄ -alkoxy)-(thio)phosphoryl,

Y represents nitrogen or a CH group and

Z represents cyano or nitro.

The invention relates, in particular, to compounds of the formula (I) inwhich

R¹ represents a five- or six-membered heterocyclic grouping from theseries comprising pyrazoyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl,thiazolyl, isothiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrazinyl andpyrimidinyl, which is optionally substituted by fluorine, chlorine,bromine, cyano, nitro, C₁ -C₂ -alkyl (which is optionally substituted byfluorine and/or chlorine), C₁ -C₂ -alkoxy (which is optionallysubstituted by fluorine and/or chlorine), C₁ -C₂ -alkylthio (which isoptionally substituted by fluorine and/or chlorine) or C₁ -C₂-alkylsulphonyl (which is optionally substituted by fluorine and/orchlorine),

R² represents C₁ -C₄ -hydroxyalkyl, dihydroxy-C₁ -C₄ -alkyl, C₁ -C₃-alkoxy-C₁ -C₃ -alkyl or di-(C₁ -C₃ -alkoxy)-C₁ -C₃ -alkyl,

R³ represents hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -hydroxyalkyl,dihydroxy-C₁ -C₄ -alkyl, C₁ -C₃ -alkoxy-C₁ -C₃ -alkyl or di-(C₁ -C₃-alkoxy)-C₁ -C₃ C-alkyl or

R² and R³ together represent hydroxy-C₂ -C₃ -alkanediyl, dihydroxy-C₂-C₃ -alkanediyl, C₁ -C₃ -alkoxy-C₂ -C₃ -alkanediyl, di-(C₁ -C₃-alkoxy)-C₂ -C₃ -alkanediyl, oxo-C₂ -C₃ -alkanediyl ordioxo-C2-C3-alkanediyl,

R⁴ represents hydrogen, methyl, ethyl, allyl, propargyl, formyl, C₁ -C₈-alkylcarbonyl (which is optionally substituted by fluorine and/orchlorine), C₁ -C₈ -alkoxy-carbonyl, benzyloxycarbonyl, phenoxycarbonyl,benzyl (which is optionally substituted by fluorine or chlorine) ordi-(C₁ -C₂ -alkoxy)-(thio)phosphoryl,

Y represents nitrogen or a CH group and

Z represents cyano or nitro.

The compounds of the formula (I) are very particularly preferred inwhich

R¹ represents 6-chloro-3-pyridyl(6-chloro-pyridin-3-yl) or represents2-chloro-5-thiazolyl(2-chlorothiazol-5-yl),

R² represents hydroxymethyl, hydroxyethyl, hydroxypropyl,dihydroxyethyl, dihydroxypropyl, methoxymethyl, ethoxymethyl,methoxyethyl, ethoxyethyl, dimethoxyethyl or diethoxyethyl,

R³ represents hydrogen, methyl, ethyl, hydroxymethyl, hydroxyethyl,hydroxypropyl, dihydroxyethyl, dihydroxypropyl, methoxymethyl,ethoxymethyl, methoxyethyl, ethoxyethyl, dimethoxyethyl ordiethoxyethyl,

R² and R³ together represent oxoethane-1,2-diyl, dioxoethane-1,2-diyl,hydroxyethane-1,2-diyl, dihydroxyethane-1,2-diyl,methoxyethane-1,2-diyl, ethoxyethane-1,2-diyl, dimethoxyethane-1,2-diylor diethoxyethane-1,2-diyl,

R⁴ represents hydrogen or methyl,

Y represents nitrogen or a CH group and

Z represents cyano or nitro.

The hydrocarbon radicals, such as alkyl, which are mentioned above inthe definition of the compounds of the general formula (I) according tothe invention are--also in combination with heteroatoms as in alkoxy--asfar as possible in each case straight-chain or branched.

Generally, halogen represents fluorine, chlorine, bromine or iodine,preferably fluorine, chlorine or bromine, in particular fluorine orchlorine.

The above-listed general radical definitions or clarifications, or thoselisted in the preference ranges, are valid in a corresponding manner forthe end products of the formula (I) as well as for the startingcompounds and intermediates.

The radical definitions can be combined together as required,consequently also between the respective preference ranges.

Examples of the compounds of the formula (I) are listed in Table 1below. ##STR4##

                                      TABLE 1                                     __________________________________________________________________________    Examples of the compounds of the formula (I)                                  R.sup.1   R.sup.2   R.sup.3                                                                              R.sup.4                                                                           Y   Z                                          __________________________________________________________________________              CH.sub.2 CH(OCH.sub.3).sub.2                                                            H      H   N   NO.sub.2                                    ##STR5## CH.sub.2 CH(OCH.sub.3).sub.2                                                            H      H   N   NO.sub.2                                    ##STR6## CH.sub.2 OH                                                                             H      H   N   NO.sub.2                                    ##STR7## CH.sub.2 CH(OCH.sub.3).sub.2                                                            H      CH.sub.3                                                                          N   NO.sub.2                                    ##STR8## CH.sub.2 CH.sub.2 OH                                                                    H      H   N   NO.sub.2                                    ##STR9## CH.sub.2 OH                                                                             CH.sub.2 OH                                                                          H   N   NO.sub.2                                    ##STR10##                                                                              CH.sub.2 CH(OC.sub.2 H.sub.5).sub.2                                                     H      H   N   NO.sub.2                                    ##STR11##                                                                              CH.sub.2 CH(OC.sub.2 H.sub.5).sub.2                                                     H      H   N   NO.sub.2                                    ##STR12##                                                                              CH.sub.2 CH(OCH.sub.3).sub.2                                                            H      H   N   NO.sub.2                                    ##STR13##                                                                              CH.sub.2 CH(OCH.sub.3).sub.2                                                            H      H   CH  CN                                          ##STR14##                                                                              CH.sub.2 CH(OCH.sub.3).sub.2                                                            H      H   N   CN                                          ##STR15##                                                                              CH.sub.2 CH(OCH.sub.3).sub.2                                                            H      H   N   CN                                          ##STR16##                                                                               ##STR17##       H   CH  NO.sub.2                                    ##STR18##                                                                               ##STR19##                                                                              H      N   CN                                              ##STR20##                                                                               ##STR21##                                                                              H      CH  CN                                              ##STR22##                                                                               ##STR23##                                                                              H      N   NO.sub.2                                        ##STR24##                                                                               ##STR25##                                                                              H      CH  NO.sub.2                                        ##STR26##                                                                               ##STR27##                                                                              H      N   CN                                              ##STR28##                                                                               ##STR29##                                                                              H      CH  NO.sub.2                                       __________________________________________________________________________

If, for example, 1-(2-thiazol-5-yl-methyl)-2-cyano-guanidine andchloroacetaldehyde dimethyl acetal are used as starting compounds, thecourse of the reaction in the process (a) according to the invention canthen be represented by the following formula diagram: ##STR30## If, forexample,1-(6-chloro-pyridin-3-yl-methyl)-1-(2,2-dimethoxyethyl)-2-nitro-guanidineis used as the starting compound, the course of the reaction in theprocess (b) according to the invention can then be represented by thefollowing formula diagram: ##STR31## If, for example,1-(2-chloro-thiazol-5-yl-methyl)-2-nitromethylene-5-oxo-imidazolidineand sodium borohydride are used as the starting compounds, the course ofthe reaction in the process (c) according to the invention can then berepresented by the following formula diagram: ##STR32## If, for example,1-(6-chloro-pyridin-3-yl-methyl)-2-cyanomethylene-4-methoxy-imidazolineand hydrogen bromide are used as the starting compounds, the course ofthe reaction in the process (d) according to the invention can then berepresented by the following formula diagram: ##STR33## If, for example,1-(6-chloro-pyridin-3yl-methyl)-2-nitroimino-3-ethyl-5-hydroxy-imidazolidineand ethyl bromide are used as the starting compounds, the course of thereaction in the process (e) according to the invention can then berepresented by the following formula diagram: ##STR34## If, for example,1-(6-chloro-pyridin-3-yl-methyl)-1-(2,2-dimethoxyethyl)-2-nitro-guanidineand methyl bromide are used as the starting compounds, the course of thereaction in the process (f) according to the invention can then berepresented by the following formula diagram: ##STR35##

The azoalkanes which are to be used as starting compounds in the process(a) according to the invention for preparing compounds of the formula(I) are generally defined by the formula (II).

In formula (II), R¹, Y and Z preferably or in particular have thosemeanings which have already been indicated above, in connection with thedescription of the compounds of the formula (I) according to theinvention, preferably or as in particular preferred for R¹, Y and Z

The starting compounds of the formula (II) are known and/or can beprepared by processes which are known per se (compare EP-A 302389, EP-A306696, EP-A 364844, EP-A 375907, EP-A 376297, EP-A 381130, EP-A 418199,EP-A 425978, EP-A 428941, EP-A 452782).

The halogen compounds which are additionally to be used as startingcompounds in the process (a) according to the invention for preparingcompounds of the formula (1) are generally defined by the formula (IIIa)and the formula (IIIb).

In formula (IIIa) and formula (IIIb), R² and R³ preferably or inparticular have those meanings which have already been indicated above,in connection with the description of the compounds of the formula (I)according to the invention, preferably or as in particular preferred forR² and R³ ; X in each case preferably represents chlorine or bromine.

The starting compounds of the formulae (IIIa) and (IIIb) are knownchemicals for organic synthesis.

All acid binding agents which are customarily used for reactions of thisnature may be employed as acid acceptors in the process (a) according tothe invention. Those which are preferably used are alkali metal andalkaline earth metal hydrides, such as lithium, sodium, potassium andcalcium hydride, alkali metal and alkaline earth metal hydroxides, suchas lithium, sodium, potassium and calcium hydroxide, alkali metal andalkaline earth metal carbonates and hydrogen carbonates, such assodiumand potassium carbonate or hydrogen carbonate, and calciumcarbonate, alkali metal acetates, such as sodium and potassium acetate,alkali metal alcoholates, such as sodium and potassium methylate,ethylate, propylate, isopropylate, butylate, isobutylate andtert-butylate, and in addition basic nitrogen compounds, such astrimethylamine, triethylamine, tripropylamine, tributylamine,diisobutylamine, dicyclohexylamine, ethyldiisopropylamine,ethyldicyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamine,N,N-dimethylbenzylamine, N,N-dimethyl-analine, pyridine, 2-methyl-,3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 2-ethyl-, 4-ethyl-and 5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo-[4,3,0]-non-5-ene (DBN),1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) and1,4-diazabicyclo-[2,2,2]-octane (DABCO).

The process (a) according to the invention is optionally carried out inthe presence of a catalyst. Suitable catalysts in this context are, inparticular, alkali metal salts such as potassium chloride, rubidiumchloride and caesium chloride.

The process (a) according to the invention for preparing the novelcompounds of the formula (I) is preferably carried out using diluents.In this context, practically all inert organic solvents are suitablediluents. These preferably include aliphatic and aromatic, optionallyhalogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane,petroleum ether, benzinc, ligroin, benzene, toluene, xylene, methylenechloride, ethylene chloride, chloroform, carbon tetrachloride,chlorobenzene and o-dichlorobenzene, ethers, such as diethyl and dibutylether, glycol dimethyl ether and diglycol dimethyl ether,tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl,methyl isopropyl and methyl isobutyl ketone, esters, such as methylacetate and ethyl acetate, nitriles, such as, e.g., acetonitrile andpropionitrile, amides, such as, e.g., dimethylformamide,dimethylacetamide and N-methylpyrrolidone, as well as dimethylsulphoxide, tetramethylene sulphone and hexamethylphosphoric triamide.

In the process (a) according to the invention, the reaction temperaturesmay be varied over a relatively wide range. In general, temperatures ofbetween 0° C. and 200° C., preferably temperatures of between 20° C. and150° C., are employed.

The process (a) according to the invention is generally carried outunder atmospheric pressure. However, it is also possible for it to becarried out under elevated or reduced pressure.

For carrying out the process (a) according to the invention, thestarting materials which are required in each case are generallyemployed in approximately equimolar quantities. However, it is alsopossible to use one of the two components which are employed in eachcase in a relatively large excess. The reactions are generally carriedout in a suitable diluent in the presence of an acid acceptor andoptionally in the presence of a catalyst, and the reaction mixture isstirred for several hours at the temperature which is required in eachcase. In the process (a) according to the invention, the working up iseffected in each case according to customary methods (compare thepreparation examples).

The compounds which are to be used as starting compounds in the process(b) according to the invention are generally defined by the formula (I),with the proviso that R² or R³ represents dialkoxyalkyl. In this case,the radicals R¹, R², R³, R⁴, Y and Z preferably or in particular havethose meanings which have already been indicated above, in the scope ofthe description of the compounds of the formula (I) according to theinvention, preferably or as in particular preferred.

The above-described starting compounds of the formula (I) for process(b) are novel compounds according to the invention; they can be preparedby the process (a) according to the invention.

The process (b) according to the invention is optionally carried out inthe presence of a reaction aid. Suitable reaction aids in this contextare in particular Lewis acids, such as boron trifluoride or aluminiumtrichloride, but also mineral acids, such as hydrochloric acid,sulphuric acid, methanesulphonic acid, benzenesulphonic acid andp-toluenesulphonic acid.

The process (b) according to the invention is preferably carried outusing a diluent. In this context, those diluents are suitable which havealready been mentioned in the description of the process (a) accordingto the invention. In addition, water, and alcohols, such as methanol,ethanol, n- or i-propanol and n-, i-, s- or t-butanol, can alsoadvantageously be used as diluents in process (b).

In the process (b) according to the invention, the reaction temperaturescan be varied over a relatively wide range. In general, temperatures ofbetween 20° C. and 150° C., preferably temperatures of between 40° C.and 100° C., are employed.

The process (b) according to the invention is generally carried outunder atmospheric pressure. However, it is also possible for it to becarried out under elevated or reduced pressure.

For carrying out the process (b) according to the invention, thereaction components are generally mixed at room temperature and thenstirred at the required temperature until the end of the reaction. Theworking up can then take place according to customary methods (comparethe preparation examples).

The compounds which are to be used as starting compounds in the process(c) according to the invention are generally defined by the formula (I),with the proviso that R² R³ together represent oxoalkanediyl. In thiscase, the radicals R¹, R², R³, R⁴, Y and Z preferably or in particularhave those meanings which have already been indicated above, in thescope of the description of the compounds of the formula (I) accordingto the invention, preferably or as in particular preferred.

The above-described starting compounds of the formula (I) for process(c) are novel compounds according to the invention; they can be preparedby the process (a) according to the invention.

The process (c) according to the invention is carried out using ahydrogenating agent. Appropriate agents in this context are, inparticular, the metal hydride complexes, such as lithium borohydride(LiBH₄), lithium aluminium hydride (LiAlH₄) and sodium borohydride(NaBH₄), which are suitable for hydrogenating carbonyl compounds tohydroxy compounds.

Process (c) is optionally carried out in the presence of a reaction aid.Suitable reaction aids in this context are, in particular, acids, suchas hydrochloric acid, sulphuric acid or acetic acid.

Process (c) is preferably carried out using a diluent. In this context,those diluents are preferably suitable which have already been mentionedin the description of the process (a) according to the invention. Inaddition, water, alcohols, such as methanol, ethanol, n- and i-propanol,and additionally also carboxylic acids, such as acetic acid andpropionic acid, can also advantageously be used as diluents in process(c).

In the process (c) according to the invention, the reaction temperaturesmay be varied over a relatively wide range. In general, temperatures ofbetween -20° C. and +50° C., preferably temperatures of between 0° C.and +30° C., are employed.

The process (c) according to the invention is generally carried outunder atmospheric pressure. However, it is also possible to carry it outunder elevated or reduced pressure.

For carrying out the process (c) according to the invention, thestarting compounds which are required in each case are generallyemployed in approximately equimolar quantities. Bowever, it is alsopossible to use one of the two components employed in each case in arelatively large excess. The reactions are generally carried out in asuitable diluent in the presence of a reaction aid, and the reactionmixture is stirred at the temperature which is required in each case.The working up in the process (c) according to the invention is effectedin each case according to customary methods (compare the preparationexamples).

The compounds which are to be used as starting compounds in the process(d) according to the invention are generally defined by the formula (I),with the proviso that R² and R³ together represent akoxyalkanediyl ordialkoxyalkanediyl. In this case, the radicals R¹, R², R³, R⁴, Y and Zpreferably or in particular have those meanings which have already beenindicated above, in the scope of the description of the compounds of theformula (I) according to the invention, preferably or as in particularpreferred.

The above-described starting compounds of the formula (I) for process(d) are novel compounds according to the invention; they can be preparedby the processes (a) or (b) according to the invention.

The process (d) according to the invention is carried out in thepresence of a hydrogen halide and/or an alkali metal halide. Preferably,hydrogen chloride or hydrogen bromide, and/or corresponding sodium orpotassium halides, that is sodium or potassium chloride or bromide, areemployed.

Process (d) is preferably carried out using a diluent. Besides water,those diluents are preferably suitable in this context which havealready been mentioned in the description of the process (a) accordingto the invention.

In the process (d) according to the invention, the reaction temperaturescan be varied over a relatively wide range. In general, temperatures ofbetween 0° C. and 100° C., preferably temperatures of between 20° C. and80° C., are employed.

The process (d) according to the invention is generally carried outunder atmospheric pressure. However, it is also possible to carry it outunder elevated or reduced pressure.

For carrying out the process (d) according to the invention, thestarting materials which are required in each case are generallyemployed in approximately equimolar quantities. However it is alsopossible to use one of the two components which are employed in eachcase in a relatively large excess. The reactions are generally carriedout in a suitable diluent, and the reaction mixture is stirred forseveral hours at the temperature which is necessary in each case Theworking up in the process (d) according to the invention is in each caseeffected according to customary methods (compare the preparationexamples).

The compounds which are to be used as starting compounds in the process(e) according to the invention are generally defined by the formula (I),with the proviso that R² and R³ together represent hydroxyalkanediyl ordihydroxyalkanediyl In this case, the radicals R¹, R², R³, R⁴, Y and Zpreferably have those meanings which have already been indicated above,in the scope of the description of the compounds of the formula (I)according to the invention, preferably or as in particular preferred.

The above-described starting compounds of the formula (I) for process(e) are novel compounds according to the invention; they can be preparedby the processes (c) or (d) according to the invention.

The alkylating agents which are additionally to be used as startingcompounds in the process (e) according to the invention for preparingcompounds of the formula (I) are generally defined by the formula (IV).

In formula (IV)

R preferably represents C₁ -C₄ -alkyl, in particular methyl or ethyl,and

X preferably represents chlorine, bromine or iodine, or the grouping--O--SO₂ --O R, in which R has the above-mentioned meaning.

The starting compounds of the formula (IV) are known chemicals fororganic synthesis.

The process (e) according to the invention is preferably carried out inthe presence of an acid acceptor. In this context, those acid bindingagents are preferably suitable which have been mentioned above in thedescription of the process (a) according to the invention.

The process (e) according to the invention is preferably carried outusing a diluent. In this context, those diluents are preferably suitablewhich have been mentioned above in the description of the process (a)according to the invention.

In the process (e) according to the invention, the reaction temperaturescan be varied over a relatively wide range. In general, temperatures ofbetween 0° C. and 150° C., preferably temperatures of between 20° C. and100° C., are employed.

The process (e) according to the invention is generally carried outunder atmospheric pressure. However, it is also possible to carry it outunder elevated or reduced pressure.

For carrying out the process (e) according to the invention, thestarting compounds which are required in each case are generallyemployed in approximately equimolar quantities. However, it is alsopossible to use one of the two components which are employed in eachcase in a relatively large excess. The reactions are generally carriedout in a suitable diluent in the presence of an acid acceptor, and thereaction mixture is stirred for several hours at the temperature whichis necessary in each case. The working up in the process (e) accordingto the invention is in each case effected according to customary methods(compare the preparation examples).

The compounds to be used as starting compounds in the process (f)according to the invention are generally defined by the formula (I),with the proviso that R⁴ represents hydrogen In this case, the radicalsR¹, R², R³, Y and Z preferably or in particular have those meaningswhich have already been indicated above, in the scope of the descriptionof the compounds of the formula (I) according to the invention,preferably or as in particular preferred.

The above-described starting compounds of the formula (I) for process(f) are novel compounds according to the invention; they can be preparedby the processes (a) to (d) according to the invention.

The halogen compounds which are additionally to be used as startingcompounds in the process (f) according to the invention for preparingcompounds of the formula (I) are generally defined by the formula (V).

In formula (V), R⁴ preferably or in particular has that meaning whichhas already been indicated above, in connection with the description ofthe compounds of the formula (I) according to the invention, preferablyor as in particular preferred for R⁴ ;

X preferably represents fluorine, chlorine, bromine or iodine, inparticular chlorine or bromine.

The starting compounds of the formula (V) are known chemicals fororganic synthesis.

The process (f) according to the invention is preferably carried out inthe presence of an acid acceptor. In this context, those acid bindingagents are preferably suitable which have been mentioned above in thedescription of the process (a) according to the invention.

The process (f) according to the invention is preferably carried outusing a diluent. In this context, those diluents are preferably suitablewhich have been mentioned above in the description of the process (a)according to the invention.

In the process (f) according to the invention, the reaction temperaturescan be varied over a relatively wide range. In general, temperatures ofbetween 0° C. and 150° C., preferably temperatures of between 20° C. and100° C., are employed.

The process (f) according to the invention is generally carried outunder atmospheric pressure. However, it is also possible to carry it outunder elevated or reduced pressure.

For carrying out the process (f) according to the invention, thestarting compounds which are required in each case are generallyemployed in approximately equimolar quantities. However, it is alsopossible to use one of the two components which are employed in eachcase in a relatively large excess, the reactions are generally carriedout in a suitable diluent in the presence of an acid acceptor, and thereaction mixture is stirred for several hours at the temperature whichis required in each case. The working up in the process (f) according tothe invention is in each case effected according to customary methods.

While being well-tolerated by plants and having favourable toxicity towarm-blooded animals, the active compounds are suitable for controllinganimal pests, in particular insects, arachnida and nematodes, which areencountered in agriculture, in forestry, in the protection of storedproducts and of materials, and in the hygiene field. They are activeagainst normally sensitive and resistant species and against all orindividual stages of development. The abovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Phylloxera vastatrix,Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. andLinognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp. Psylla spp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus andLatrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyommaspp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The phytoparasitic nematodes include Pratylenchus spp., Radopholussimilis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heteroderaspp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinemaspp. and Trichodorus spp.

The active compounds of the formula (I) according to the invention aredistinguished by outstanding insecticidal activity. They exhibit a verystrong action both as leaf insecticides and as ground insecticides, e.g.against beetle larvae (e.g. Phaedon cocheariae), against rice leafhoppers (e.g. Nephotettix cincticeps) and against leaf aphids (e.g.Myzus persicae and Aphis fabae).

The active compounds of the formula (I) according to the invention arealso suitable for combating arthropods which infest agriculturalproductive livestock such as, for example, cattle, sheep, goats, horses,pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geeseand bees, other pets, such as, for example, dogs, cats, cage birds andaquarium fish, and also so-called test animals, such as, for example,hamsters, guinea pigs, rats and mice. By combating these anthropodscases of death and reductions in productivity (for meat, milk, wool,hides, eggs, honey etc.) should be diminished, so that a more economicand simpler animal husbandry is possible by use of the active compoundsaccording to the invention.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boli, the feed-through process and suppositories, by parenteraladministration, such as, for example, by injections (intra-muscular, bynasal administration, by dermal use in the form, for example, of dippingor bathing, spraying, pouring on and spotting on), washing andpowdering, and also with the aid of shaped articles containing theactive compound, such as collars, ear tags, tail tags, limb bands,halters, marking devices, etc.

Depending on their particular phydical and/or chemical oak shafts, theactive compounds can be converted to the customary formulations, such assolutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols, natural and synthetic materials impregnated with activecompound, very fine capsules in polymeric substances and in coatingcompositions for seed, and furthermore in formulations used with burningequipment, such as fumigating cartridges, fumigating cans, fumigatingcoils and the like, as well as ULV cold mist and warm mist formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers an optionally with the useof surface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water as aextender, organic solvents can, for example, also be used as auxiliarysolvents. As liquid solvents, there are suitable in the main: aromatics,such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics orchlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at ambient temperature andunder atmospheric pressure, for example aerosol propellant, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide; as solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silica, alumina and silicates; assolid carriers for granules there are suitable: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,maize cobs and tobacco stalks; as emulsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumen hydrolysis products; asdispersing agents there are suitable: for example ligninsulphite wasteliquors and methylcellulose.

Adhesives such as carboxy-methylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present intheiricommercially available formulations and in the use formst preparedfrom these formulations, as a mixture with other active compounds, suchas insecticides, attractants, sterilizing agents, acaricides,nematicides, fungicides, growth-regulating substances or herbicides. Theinsecticides include, for example, phosphates, carbamates, carboxylates,chlorinated hydrocarbons, phenylureas, substances produced bymicroorganisms inter alia.

The active compounds according to the invention can furthermore bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with synergisticagents. Synergistic agents are compounds which increase the action ofthe active compounds, without it being necessary for the synergisticagent added to be active itself.

The active compound content, of the use forms-prepared from thecommercially available formulations, can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

Application is effected in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompounds are distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

Preparation Examples EXAMPLE 1 ##STR36## <Process (a)>

A mixture of 1.15 g (5.0 mmol) of1-(6-chloro-pyridin-3-yl-methyl)-2-nitroguanidine, 0.76 g (5.5 mmol) ofpotassium carbonate, 0.09 g (0.5 mmol) of caesium chloride, 0.92 ml (5.5mmol) of bromoacetaldehyde diethyl acetal and 5 ml of dimethylformamideis heated to 125° C. while stirring, and stirred at this temperature fortwo hours. After the addition of a further 0.76 g (5.5 mmol) ofpotassium carbonate and a further 0.92 ml (5.5 mmol) ofbromoacetaldehyde diethyl acetal, the mixture is stirred at 125° C. fora further two hours.

After cooling to room temperature, the mixture is then diluted with icewater to about four times the volume, and extracted with methylenechloride. The organic phase is dried with sodium sulphate, and filtered.The filtrate is concentrated and the residue is digested with ice-coldcyclohexane. The syrupy crude product which remains undissolved duringthis process is purified by column chromatography (silica gel; methylenechloride|ethyl acetate 1:1).

0.16 g (9% of theory) of1-(6-chloro-pyridin-3-yl-methyl)-1-(2,2-diethoxyethyl)-2-nitro-guanidineare thus obtained as an amorphous 2nd fraction.

¹ H-NMR (CDCl₃,δ): --CH(OC₂ H₅)₂ 4.59 ppm (triplet) --CH₂ --CH(OC₂ H₅)₂3.39 ppm (doublet)

EXAMPLE 2 ##STR37## <Process (b)>

A mixture of 1.45 g (4.2 mmol) of1-(6-chloro-pyridin-3-yl-methyl)-1-(2,2-diethoxy-ethyl)-2-nitro-guanidineand 44 ml of ethanol is heated to 78° C. and, after the addition of0.725 ml (7.25 mmol) of concentrated hydrochloric acid, is stirred atthis temperature for 15 minutes.

After cooling to room temperature, the mixture is diluted with ethylacetate to about three times the volume, and neutralised with aqueouspotassium hydrogen carbonate solution. The organic phase is separatedoff, dried with sodium sulphate and filtered. The filtrate isconcentrated and the residue is purified by column chromatography(silica gel; methylene chloride|methanol 15:1).

1.2 g (95% of theory) of1-(6-chloro-pyridin-3-yl-methyl)-2-nitroimino-4-ethoxy-imidazolidine areobtained as an amorphous 2nd fraction.

¹ H-NMR (DMSO₃, δ): 4-CH 5.90 ppm 5-CH.sub. 2 3.70 ppm (multiplet)

EXAMPLE 3 ##STR38## <Process (c)>

4.2 g (15.5 mmol) of1-(6-chloro-pyridin-3-yl-methyl)-2-nitroimino-5-oxo-imidazolidine aredissolved in 495 ml of tetrahydrofuran, and 25.2 ml (25.2 mmol of HCl)of 1N hydrochloric acid are then added to this solution.

The mixture is cooled to 15° C., and 42 ml of a 4% strength aqueoussolution of sodium borohydride are added dropwise to it at thistemperature. After stirring subsequently for 30 minutes, the solution isdecanted off from the undissolved solid and concentrated. 200 ml ofsaturated aqueous sodium chloride solution are then added, and themixture is extracted three times with 200 ml of ethyl acetate on eachoccasion.

The combined organic phases are dried with sodium sulphate and filtered.The filtrate is concentrated, the residue is digested with 200 ml ofethyl acetate|acetonitrile (10:1), and the product which remainsundissolved is isolated by filtering off with suction.

1st product fraction:

0.6 g of brown-yellow crystals. The filtrate is fractionated on a silicagel column.

2nd product fraction:

2.8 g of colourless crystals; Melting-point: 192° C. Total yield: 3.4 g(80% of theory) of1-(6-chloro-pyridin-3-yl-methyl)-2-nitroimino-5-hydroxy-imidazolidine.

EXAMPLE 4 ##STR39## <Process (d)>

A mixture of 0.36 g (1.2 mmol) of 1-(6-chloro-pyridin3-yl-methyl-2-nitroimino-4-ethoxy-imidazolidine, 36 ml oftetrahydrofuran, 36 ml of saturated aqueous sodium chloride solution and2.4 ml of 1N hydrochloric acid is stirred at 45° C. for 105 minutes.

After cooling to room temperature, the two-phase reaction mixture isadjusted to pH 8 using potassium hydrogen carbonate solution, and isthen extracted three times with ethyl acetate the combined extracts aredried with sodium sulphate and filtered. The filtrate is concentrated,the residue is digested with diethyl ether, and the resultantcrystalline product is isolated by filtration with suction.

0.143 g (44% of theory) of1-(6-chloro-pyridin-3-yl-methyl)-2-nitroimino-4-hydroxy-imidazolidineare obtained with a melting point of 170° C.

EXAMPLE 5 ##STR40## <Process (e)>

1.1 g (4.0 mmol) of1-(6-chloro-pyridin-3-yl-methyl)-2-nitroimino-5-hydroxy-imidazolidineare dissolved in 10 ml of dimethylformamide, and 0.24 g (8.0 mmol) ofsodium hydride are then added in portions to this solution whilestirring. The mixture is stirred at 15° C. for 30 minutes. 0.5 ml (8.0mmol) of methyl iodide are then added dropwise at +5° C. and thereaction mixture is stirred at 20° C. for 2 hours. Subsequently, themixture is diluted with water to about three times the volume, and thenextracted three times with ethyl acetate. The combined extracts aredried with sodium sulphate and filtered. The filtrate is concentratedand the residue is fractionated by column chromatography (silica gelethyl|acetate).

0.80 g (67% of theory) of1-(6-chloro-pyridin-3-yl-methyl)-2-nitroimino-3-methyl-5-methoxy-imidazolidineare obtained as an amorphous 3rd fraction.

¹ H-NMR(CDCl₃,) OCH₃ 3.26 ppm (singlet) NCH₃ 3.01 ppm (singlet)

The compounds of the formula (I) listed in Table 2 below can also, forexample, be prepared in analogy with the Preparation Examples 1 to 5 andin accordance with the general description of the preparation processesaccording to the invention. ##STR41##

                                      TABLE 2                                     __________________________________________________________________________    Preparation examples for the compounds of the                                 formula (I)                                                                   Ex.                                        Physical                           No.:                                                                             R.sup.1  R.sup.2   R.sup.3     R.sup.4                                                                          Y  Z  Data                               __________________________________________________________________________                           ##STR42##  H  N  NO.sub.2                                                                         m.p.: 173° C.               7                                                                                 ##STR43##                                                                                        ##STR44##  H  N  NO.sub.2                                                                         m.p.: 185° C.               8                                                                                 ##STR45##                                                                             CH.sub.2 CH(OC.sub.2 H.sub.5).sub.2                                                     CH.sub.2 CH(OC.sub.2 H.sub.5).sub.2                                                       H  N  NO.sub.2                                                                         (amorph.)                          9                                                                                 ##STR46##                                                                             CH.sub.2 CH(OCH.sub.3).sub.2                                                            H           H  N  NO.sub.2                                                                         (amorph.)                          10                                                                                ##STR47##                                                                                        ##STR48##  H  N  NO.sub.2                                                                         (amorph.)                          11                                                                                ##STR49##                                                                                        ##STR50##  CH.sub.3                                                                         N  NO.sub.2                                                                         (amorph.)                          12                                                                                ##STR51##                                                                                        ##STR52##  H  N  NO.sub.2                                                                         m.p.: 127° C.               13                                                                                ##STR53##                                                                                        ##STR54##  H  N  NO.sub.2                                                                         (amorph.)                          __________________________________________________________________________

Application Examples EXAMPLE A

Phaedon larvae test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of the active compound of the desired concentration and areinfested with mustard beetle larvae (Phaedon cochleariae), as long asthe leaves are still moist.

After the desired time, the destruction in % is determined. 100% meansthat all the beetle larvae have been killed; 0% means that none of thebeetle larvae have been killed.

In this test, the compounds obtained according to the PreparationExamples (1), (3), (5) and (6), for example, exhibit, at a concentrationof active compound of 0.1%, a 100% destruction of the test animals after7 days.

EXAMPLE B

Nephotettix test

Solvent 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Rice seedlings (Oryza sativa) are treated by being dipped into thepreparation of the active compound of the desired concentration and areinfested with larvae of the green rice leafhopper (Nephotettixcincticeps), as long as the seedlings are still moist.

After the desired time, the destruction in % is determined. 100% meansthat all the leafhoppers have been killed; 0% means that none of theleafhoppers has been killed.

In this test, the compounds obtained according to the PreparationExamples (1), (3), (5) and (8), for example, exhibit, at a concentrationof active compound of 0.1%, a 100% destruction of the test animals after6 days.

EXAMPLE C

Myzus test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea), which are strongly infested with thegreen peach aphid (Myzus persicae), are treated by being dipped into thepreparation of the active compound of the desired concentration.

After the desired time, the destruction in % is determined. 100% meansthat all the test insects have been killed; 0% means that none of theaphids has been killed.

In this test, the compounds obtained according to the PreparationExamples (1) and (5), for example, exhibit, at a concentration of activecompound of 0.1%, a 100% destruction of the test animals after 6 days.

EXAMPLE D

Aphis test (systemic action)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Bean plants (Vicia faba) which have been heavily infested with the blackbean aphid (Aphis fabae) are each watered with 20 ml of the preparationof the active compound of the desired concentration in such a way thatthe preparation of the active compound penetrates into the soil withoutwetting the shoot. The active compound is taken up by the roots andpassed to the shoot.

After the desired time, the destruction in % is determined. 100% meansthat all the test insects have been killed; 0% means that none of thetest insects has been killed.

In this test, the compounds obtained according to the PreparationExamples (3) and (5), for example, exhibit, at a concentration of activecompound of 0.1%, a 100% destruction of the test animals after 4 days.

EXAMPLE E

Critical concentration test/root-systemic action

Test insect: Myzus persicae

Solvent: 4 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, B1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is intimately mixed with soil. Theconcentration of the active compound in the preparation is ofpractically no importance, only the amount by weight of active compoundper unit volume of soil, which is given in ppm (=mg/l), being decisive.The treated soil is transferred into pots and these are planted withcabbage (Brassica oleracea). The active compound can in this way betaken up from the soil by the roots of the plants and be transportedinto the leaves.

To demonstrate the root-systemic effect, the leaves are infested withthe abovementioned test insects after 7 days. After a further 2 days,the evaluation is made by counting or estimating the dead insects Theroot-systemic action of the active compound is deduced from themortality figures. It is 100% if all test animals have been killed and0% if just as many test insects are still alive as in the case of theuntreated control.

In this test, the compounds obtained according to the PreparationExamples (1) and (3), for example, exhibit, at a concentration of activecompound of 20 ppm, a 100% destruction of the test animals.

EXAMPLE F

Blowfly larvae test

Test animals: Lucilia cuprina larvae

Emulsifier: 35 parts by weight of ethylene glycol monomethyl ether 35parts by weight of nonylphenol polyglycol ether

To produce a suitable preparation of active compound, three parts byweight of active compound are mixed with seven parts by weight of theabovementioned mixture, and the emulsion concentrate thus obtained isdiluted with water to the desired concentration in each case.

About 20 Lucilia cuprina res. larvae are placed in a test tube, whichcontains about 1 cm³ of horse meat and 0.5 ml of the preparation of theactive compound. After 24 hours, the effectiveness of the preparation ofthe active compound is determined. 100% means that all the blowflylarvae have been killed; 0% means that no blowfly larvae have beenkilled.

In this test, the compounds according to the Preparation Examples (1),(2), (4), (5) and (8), for example, exhibit good effectiveness.

We claim:
 1. A substituted diazacyclohexane of the formula ##STR55## in which, R¹ is a five- or six membered heterocyclic grouping which independently contains 1, 2, 3 or 4 nitrogen atoms, and one or two oxygen atoms or sulphur atoms as the heteroatom ring members--the number of heteroatoms being 1, 2, 3 or 4- and which is optionally independently substituted by at least one of halogen, cyano, nitro, alkyl, halogenoalkyl, alkenyl, halogenoalkenyl, alkinyl, alkoxy, halogenoalkoxy, alkenyloxy, halogenoalkenyloxy, alkinyloxy, alkylthio, halogenoalkylthio, alkenylthio, halogenoalkenylthio, alkinylthio, alkysulphinyl, halogenoalkylsulphinyl, alkylsulphonyl, halogenoalkylsulphonyl, amino, alkylamino, dialkylamino, aryl, arylthio, arylamino, aralkyl, formylamino, alkylcarbonylamino, formyl, carbomoyl, alkyl-carbonyl and alkoxycarbonyl,R⁴ is hydrogen, alkyl (which is optionally substituted by halogen, cyano, alkoxy, alkylthio, dialkylamino, trialkylsilyl, alkoxycarbonyl, carboxyl, carbamoyl, alkylaminocarbonyl or dialkylaminocarbonyl, or by the radical R¹, where R¹ has the abovementioned meaning), alkenyl (which is optionally substituted by halogen), alkinyl, benzyl (which is optionally substituted by halogen, cyano, nitro, alkyl, halogenoalkyl, alkoxy or alkoxycarbonyl), formyl, alkylcarbonyl (which is optionally substituted by halogen, cyano, phenyl, phenoxy or alkoxy), cycloalkylcarbonyl (which is optionally idependently substituted by at least one of halogen and alkyl), alkenylcarbonyl (which is optionally substituted by halogen), phenylcarbonyl or naphthylcarbonyl (which are optionally substituted by halogen, alkyl, halogenoalkyl, cyano, nitro, alkoxy and/or alkoxy-carbonyl), alkoxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl, alkylthiocarbonyl, benzylthiocarbonyl, phenylthiocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, phenylaminocarbonyl (which is optionally substituted by halogen, cyano, nitro, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio or alkoxycarbonyl), benzoylaminocarbonyl (which is optionally substituted halogen, alkyl or halogenoalkyl), phenylsulphonylaminocarbonyl (which is optionally substituted by halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy or alkoxycarbonyl), alkylthio (which is optionally substituted by halogen), phenylthio (which is optionally substituted by halogen, nitro or alkyl), alkylsulphinyl, alkylsulphonyl (which is optionally substituted by halogen), phenylsulphinyl (which is optionally substituted by halogen, nitro or alkyl), phenylsulphonyl or naphthylsulphonyl (which are optionally independently substituted by halogen, cyano, nitro, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy and alkoxycarbonyl), dialkyl(thio)phosphoryl, alkyl-alkoxy(thio)phosphoryl or dialkoxy(thio)phosphoryl, Y is nitrogen or a CH group, Z is cyano or nitro, and Q is at least one member selected from the group consisting of alkoxy and oxo.
 2. A substituted diazacyclohexane according to claim 1, in whichR¹ is 6-chloro-3-pyridyl or 2-chloro-5-thiazolyl, and R⁴ is hydrogen or methyl.
 3. An insecticidal composition comprising an insecticidally effective amount of a compound according to claim
 1. 4. A method of combating insects which comprises applying to such insects or to an insect habitat an insecticidally effective amount of a compound according to claim 1, and a carrier.
 5. A substituted diazacyclohexane according to claim 1, in whichR¹ is a five- to six-membered heterocyclic radical selected from the group consisting of furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3- or 1,2,4-triazolyl, oxazolyl, isoxazolyl, 1,2,4- or 1,3,4-oxadiazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,2,4-, 1,2,5-, or 1,3,4-thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, and pyrazinyl, which is optionally independently substituted by fluorine, chlorine, bromine, iodine, cyano, nitro, C₁ -C₄ -alkyl (which is optionally independently substituted by fluorine and chlorine), C₂ -C₄ -alkenyl (which is optionally, independently substituted by fluorine and chlorine), C₂ -C₄ -alkinyl, C₁ -C₄ -alkoxy (which is optionally independently substituted by fluorine and chlorine), C₃ -C₄ -alkenyloxy (which is optionally independently substituted by fluorine and chlorine), C₃ -C₄ -alkinyloxy, C₃ -C₄ -alkylthio (which is optionally independently substituted by fluorine and chlorine), C₃ -C₄ -alkenylthio (which is optionally independently substituted by fluorine and chlorine), C₃ -C₄ -alkinylthio, C₁ -C₄ -alkylsulphinyl (which is optionally independently substituted by fluorine and chlorine), C₁ -C₄ -alkylsulphonyl (which is optionally independently substituted by fluorine and chlorine), amino, C₁ -C₄ -alkylamino di-(C₁ -C₄ -alkyl)-amino, phenyl, phenoxy, phenylthio, phenylamino, benzyl, formylamino, C₁ -C₄ -alkyl-carbonylamino, alkyl-carbonylamino, formyl, carbamoyl, C₁ -C₄ -alkylcarbonyl and C₁ -C₄ -alkoxycarbonyl, and R⁴ is hydrogen, C₁ -C₄ -alkyl (which is optionally substituted by fluorine, chlorine, cyano, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, di-(C₁ -C₄ -alkyl)-amino, trimethylsilyl, C₁ -C₄ -alkoxy-carbonyl, carboxyl, carbamoyl, C₁ -C₄ -alkyl-amino-carbonyl, di-(C₁ -C₃ -alkyl)-aminocarbonyl, or by a heterocyclic grouping as is defined above for R¹, C₂ -C₄ -alkenyl (which is optionally substituted by fluorine or chlorine), C₂ -C₄ -alkinyl, benzyl (which is optionally substituted by fluorine, chlorine, cyano, nitro, C₁ -C₂ -alkyl, trifluoromethyl, C₁ -C₂ -alkoxy or C₁ -C₂ -alkoxy-carbonyl), formyl, C₁ -C₂₀ -alkyl-carbonyl (which is optionally substituted by fluorine, chlorine, bromine, phenyl, phenoxy or C₁ -C₄ -alkoxy), C₃ -C₆ -cycloalkylcarbonyl (which is optionally independently substituted by fluorine, chlorine and C₁ -C₄ -alkyl), C₂ -C₂₀ -alkenyl-carbonyl (which is optionally independently substituted by fluorine and chlorine), phenylcarbonyl or naphthylcarbonyl (which are optionally independently substituted by fluorine, chlorine, bromine, C₁ -C₄ -alkyl, trifluorimethyl, cyano, nitro, C₁ -C₄ -alkoxy and C₁ -C₄ -alkoxy-carbonyl), C₁ -C₂₀ -alkoxy-carbonyl, benzyloxy-carbonyl, phenoxycarbonyl, C₁ -C₄ -alkylthiocarbonyl, benzylthiocarbonyl, phenylthio-carbonyl, C₁ -C₆ -alkylaminocarbonyl, di-(C₁ -C₄ -alkyl)-amino-carbonyl, phenylaminocarbonyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C₁ -C₄ -alkyl, trifluorimethyl, C₁ -C₄ -alkoxy, C₁ -C₂ -fluoroalkoxy, C₁ -C₂ -chlorofluoroalkoxy, C₁ -C₄ -alkylthio, C₁ -C₂ -fluoroalkylthio, C₁ -C₂ -chlorofluoroalkylthio or C₁ -C₄ -alkoxycarbonyl), benzoylamino-carbonyl (which is optionally substituted by fluorine, chlorine, bromine, methyl or trifluoromethyl), phenylsulphonylaminocarbonyl (which is optionally substituted by fluorine, chlorine, bromine, methyl, trifuoromethyl, C₁ -C₄ -alkoxy, C₁ -C₂ -fluoroalkoxy, C₁ -C₂ -chlorofluoroalkoxy or C₁ -C₄ -alkoxy-carbonyl), C₁ -C₄ -alkylthio (which is optionally independently substituted by fluorine and chlorine), phenylthio (which is optionally substituted by fluorine, chlorine, bromine, nitro or methyl), C₁ -C₄ -alkylsulphinyl, C₁ -C₄ -alkylsulphonyl (which is optionally independently substituted by fluorine and chlorine), phenylsulphinyl (which is optionally substituted by fluorine, chlorine, chlorine, bromine, nitro or methyl), phenylsulphonyl or naphthylsulphonyl (which are optionally independently substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, trifluoromethyl, C₁ -C₄ -alkoxy, C₁ -C₂ -fluoroalkoxy, C₁ -C₂ -chlorofluoroalkoxy and or C₁ -C₄ -alkoxy-carbonyl), dimethyl(thio)phosphoryl, C₁ -C₄ -alkyl-C₁ -C₄ -alkoxy(thio)phosphoryl or di(C₁ -C₄ -alkoxy)-(thio)phosphoryl.
 6. A substituted diazacyclohexane according to claim 5, in whichR¹ is 6-chloro-3-pyridyl or 2-chloro-5-thiazolyl.
 7. A substituted diazacyclohexane according to claim 1, in whichR¹ is a five- or six membered heterocyclic grouping selected from the group consisting of pyrazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrazinyl and pyrimidinyl, which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C₁ -C₂ -alkyl (which is optionally independently substituted by fluorine and chlorine), C₁ -C₂ -alkoxy (which is optionally independently substituted by fluorine and chlorine), C₁ -C₂ -alkylthio (which is optionally independently substituted by fluorine and chlorine) or C₁ -C₂ -alkylsulphonyl (which is optionally independently substituted by fluorine and chlorine), and R⁴ is hydrogen, methyl, ethyl, allyl, propargyl, formyl, C₁ -C₈ -alkylcarbonyl (which is optionally independently substituted by fluorine and chlorine), C₁ -C₈ -alkoxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl, benzyl (which is optionally substituted by fluorine or chlorine) or di-(C₁ -C₂ -alkoxy)-(thio)phosphoryl. 